Method of making quinone di-imides



Patented May 31, 1938 1 UNITED STATES PATENT OFFICE METHOD OF MAKING QUINONE DI-IMIDES Waldo L. Semon, Silver Lake, Ohio, assignor to The B. F. Goodrich Company, New York, N. Y., a corporation of New York No Drawing. Application October 27, 1936,'

Serial No. 107,802

7 Claims. (01. 260-56) This invention relates to the art of manufac- I have oxidized N,N' diphenyl-p-phenylene dituring organic chemicals, and has for its object to amine to N,N' diphenyl-p-benzoquinone di-imide provide an improved method for the manufacby grinding it in a mortar at room temperature ture of quinone di-imides from aromatic secondwith sodium hydroxide and cupric chloride. This ary amines. reaction works equally well when sodium car- Heretofore this reaction has been performed bonate is substituted for sodium hydroxide. I in solution, using an oxidizing agent such as an A wide variety of secondary aromatic amines alkaline potassium permanganate solution. Some will underzo this reaction. Any secondary arcof the yield was always lost during the recovery matic amine may be selected as the starting com- 10 and purification of the product. pound which falls in the class represented by 10 I have discovered that certain secondary arothe general formula: matic amines may be smoothly oxidized to H H quinone di-imides by exposing them to the air in the presence of an alkali. Since most of the R N A N R secondary amines are rather high melting solids where R is a radical selected from the class con- 5 they are most easily exposed to the air by grindsisting of aryl, alkoxyaryl, and halogen-substiing, and become converted to the quinone dituted aryl groups, and A is an arylene group imides as fast as fresh surfaces are exposed. capable of assuming a quinoid structure. By Certain materials such as copper, cobalt, iron or aryl, I mean any univalent aromatic hydrolead salts and oxides catalyze the reaction. A carbon radical, as phenyl or tolyl, whose free 20 solvent may be present, but it is a great advantage valence belongs to the nucleus and not to a side of my method that it is not needed to secure a chain. Whether the arylene group is capable of smooth reaction. assuming a quinoid structure depends upon the As a specific example of my invention, I will relative position of the nitrogen atoms. For inillustrate how I prepare N,N diphenyl-p-benzosta ce, th nitrogen atoms us be Ortho or pa quinone di-imide. I grind together in a ball to each other on a benzene nucleus and 1,2; 1,4;

mill gently heated by a small flame N,N dior 2,6 on a naphthalene nucleus.

phenyl-p-phenylene diamine 260 g. (1.0 mol.) To illustrate the wide application of this methand sodium hydroxide 10 g. (0.25 mol.) for about od, I will list some of the compounds which may six hours. The melting point first drops to 130 be prepared by this reaction. Besides the two 0 0., then rises slowly to a maximum of 180 C. heretofore mentioned, these include: N,N diphen- The product is then removed and washed with yl-o-benzoquinone di-imide; N,N-di-isobutylwater. There is secured a quantitative yield of p-phenyl-p-benzoquinone di-imide; N,N' di-p- N,N' diphenyl-p-benzoquinone di-imide. The rexenyl-p-benzoquinone di-imide; N,N'-di-a-naphaction is represented by the following: thyl-p-benzoquinone di-imide; N,N'-diphenyl- 35 40 AS ano her x p f y invention, I grind napthaquinone 2,6) di-imlde; N,N-di-p-anisy1-p- 40 N,N' di-p-naphthyl-p-phenylenediamine with a benzoquinone di-imide; N,N-diphenyl Z-phenylsmall amount of sodium hydroxide and lead benzoquinone-(1,4) di-imide; N,N'-diphenyl toluoxide, and then heat the mixture at a temperap-quinone di-imide; and N,N'-diphenyl diphenoture of about 135 C. for about eight hours. The quinone-( ,4') di-imide. All of these compounds formation of t e N D y -pbenz0- are valuable as antioxidants, as disclosed in my 45 quinone di-imide, a brick red product melting copending application, Serial No. 38,806, filed Auabove 345 C. is represented by the following: gust 31, 1935.

Heat is not essential to this method, but it In the term alkali, I wish to include the 55 causes the reacti n to proceed more v r usly. oxides, hydroxides, amides and carbonates of so- 55 migtmmwmgylqm dium and potassium as well as oxides and hydroxides of the alkaline earth metals.

I claim:

1. The method of making quinone di-imides which comprises oxidizing in the air in the presence of alkali a secondary aromatic amine of the RI I-A1 IR formula, where R is a radical selected from the class consisting of hydrocarbon aryl and alkoxy-- )7 in the presence of alkali a secondary aromatic amine of the i R-N-A-N-R formula, where R is a radical selected from the class consisting of hydrocarbon aryl and alkoxyaryl groups, and A is an arylene group capable of assuming a quinoid structure.

4. The method of making quinone di-imides which comprises oxidizing in the air in the presence of alkali a secondary aromatic amine of the R-N-A-N-R formula, where R is an hydrocarbon aryl group and A is an arylene group capable of assuming a quinoid structure.

5. The method of making quinone di-imides which comprises grinding in the air in the presence of alkali a secondary aromatic amine of the 1 1 H RNA-I1IR formula, where R is an hydrocarbon aryl group and A is an arylene group capable of assuming a quinoid structure.

6. The method of making quinone di-imides which comprises grinding and heating in the air in the presence of alkali a secondary aromatic amine of the i i R--NANR formula, where R is an hydrocarbon aryl group and A is an arylene group capable of assuming a quinoid structure.

'7. The method of making N,N' diphenyl-pbenzoquinone di-imide which consists of grinding and heating N,N' diphenyl p-phenylene diamide in the air in the presence of alkali.

WALDO L. SEMON. 

